EP0111928A1 - Katalyse von Kondensationsreaktionen - Google Patents
Katalyse von Kondensationsreaktionen Download PDFInfo
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- EP0111928A1 EP0111928A1 EP83112839A EP83112839A EP0111928A1 EP 0111928 A1 EP0111928 A1 EP 0111928A1 EP 83112839 A EP83112839 A EP 83112839A EP 83112839 A EP83112839 A EP 83112839A EP 0111928 A1 EP0111928 A1 EP 0111928A1
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- EP
- European Patent Office
- Prior art keywords
- range
- strontium
- catalyst
- group
- morpholine
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/08—Bridged systems
Definitions
- the present invention relates to organic condensation reactions effected in the presence of novel pyrophosphate and hydrogen phosphate catalysts and is more particularly concerned with the production of amine compounds in enhanced yields.
- Triethylenediamine also called diazabicyclo -[ 2 . 2 .2]- octane
- Triethylenediamine has been widely employed commercially as a catalyst in organic isocyanate reactions with compounds containing labile hydrogen, as in the production of urethane polymers.
- Triethylenediamine (sometimes hereinafter referred to as TEDA) was initially prepared in significant quantities by methods such as that described in U.S. Patent No. 2,937,176, by passing aliphatic amines in vapor phase over acidic cracking catalyst, such as silica-alumina dried gel or acid- activated clays. Numerous other feed stocks as well as other catalysts are disclosed in subsequent patents for preparation of TEDA as well as C-alkyl derivatives thereof.
- U.S.S.R. In ventor's Certificate No. 525,681 discloses that the known processes for the preparation of TEDA by the catalytic conversion of various amines use aluminosilicate cracking catalysts, alumina with different additives, tungsten oxide or phosphates of metals at temperatures of 220°C to 550°C, under pressures of 0,1 to 150 atm. (absolute), in the presence of various diluents.
- U . S . Patent 3,297,701 discloses as catalysts for preparation of TEDA and C-alkyl TEDA, in addition to the preferred aluminum phosphate stated to be superior, other phosphate compounds including calcium and iron phosphates among other listed metal phosphates.
- phosphate compounds including calcium and iron phosphates among other listed metal phosphates.
- N-aminoethylpiperazine to triethylenediamine over aluminum phosphate catalyst
- at most up to 39 mol% triethylenediamine is said to be obtained.
- Other of the named metal phosphate catalysts in the examples of the patent obtain yields of less than 10 mol% TEDA.
- Acid metal phosphate catalysts particularly phosphates of boron, aluminum and trivalent iron, have also been proposed for use in intramolecular cyclic dehydration reactions and other condensation reactions involving amino compounds. Examples of such reactions are found in U.S. Patent 4,117,227, which discloses conversion of an N-substituted diethanolamine to the corresponding N-substituted morpholine. These condensation reactions are carried out in liquid phase at a temperature of from about 190°C to about 260°C and at any pressure to maintain reactants in a liquid state, i.e. generally from about 10 to about 1000 psig.U.S.
- Patent 4,036,881 describes preparation of non-cyclic polyalkylene polyamines by condensation of an alkylene diamine with an ethanolamine.
- N-hydroxethylmorpholine is condensed with morpholine in the presence of aluminum phosphate catalyst attemperatures from about 240° to 300°C and pressures of about 200 to 500 psig to form dimorpholino ethane according to U.S. Patent 4,103,087.
- dimorpho- linodiethyl ether is obtained by condensation of hydroxyethyl morpholine with aminoethyl morpholine over iron, aluminum or boron phosphate in U.S. Patent 4,095,022.
- Reaction-of piperazine with ethanolamine over such acidic metal phosphate at a temperature of from about 250° to about 350°C and a pressure ranging from about 200 psig to about 500 psig produces N-aminoethyl piperazine according to U.S. Patent 4,049,657.
- U.K. Patent 1,492,359 discloses the preparation of morpholine compounds by reacting an aminoalkoxyalkanol compound over phosphoric acid and similar types of phosphorus-containing substances.
- Pyrophosphates of lithium, sodium, strontium and barium have been used as dehydration catalysts; see U.S. Patent 3,957,900.
- Phosphates and pyrophosphates of strontium and nickel have been used for the dehydrogenation of, for example, n-butene to butadiene under the conditions described in U.S. Patent 3,541,172.
- amines from ammonia and an alcohol over alumina, silica-alumina, silica, titania, tungstic oxides, clays or various metal phosphates of the typ referred to above at ammonia to alcohol mole ratios of from 2:1 to 6:1 depending on the ratio of amines desired, temperatures in the range of 300°C to 500°C pressures of 790 to 3550 kilopascals (100 - 500 psig), and a gas hourly space velocity of 500 to 1500 mol/mol; see Kirk-Othmer Encyclopedia of Chemical Technology third Edition, Vol. 2 (1978), page 276.
- the monohydrogen and dihydrogen phosphate catalysts of the present invention are prepared by reaction of a mono- or diphosphate of an alkali metal or ammonium with a soluble salt of strontium, copper, magnesium, calcium, barium, zinc, aluminum, lanthanum, cobalt, nickel, cerium or neodymium at ambient temperatures.
- the highest purity and best yields of the present invention are obtained when using the soluble metal salts of a strong acid such as the metal nitrates, in substantially stoichiometric proportion to the phosphate.
- the reaction mixture is at a pH of about 3.5 to 6.5.
- the ratio of phosphate to metal salt in the reaction mixture should be such as to have a pH of 5 ⁇ 3, or the mixture should be adjusted to that pH range.
- the pyrophosphate form of the catalysts of the present invention are prepared by heat treating the metal monohydrogen or dihydrogen phosphate product at temperatures above about 300°C up to 750°Cin the presence of a mixture of steam and air, preferably at least about 20% by volume of steam.
- the metal pyro-, monohydrogen or dihydrogen phosphate product may be employed in the form of irregular particles of the desired size range prepared by breaking up the washed and dried filter cake or in the form of regular shaped pellets obtained by known methods of casting or extruding or the product may be deposited or otherwise impregnated into the pores of a microporous substrate such-as alumina, silica, silica-alumina, and the like.
- substantially the same conditions may be employed as when using the known catalysts for the particular synthesis. For optimum results, however, some adjustment in temperature, diluent and/or space rate may be found beneficial.
- Some specific examples of the type of organic compounds selectively obtained by the method of this invention include TEDA, the aliphatic alkylamines such as methylamine, methylethylamine, dimethylethylamine, morpholine, and dimethylaminoethylmorpholine.
- the temperature is in the range of about 285° to 420°C
- the pressure is in the range of above 1,5 and up to 150 atmospheres
- the liquid hourly space velocity (LHSV) of the organic feed stock per volume of catalyst is in the range of about 0.05 to 1.5.
- the temperature is in the range of about 300° to 400°C
- the pressure is in the range of about 3 to 10 atmospheres
- the LHSV is in the range of about 0.1 to 0.3 to obtain the highest yields and most economical process.
- the operable ratio of the organic feeds to water diluent is about 10 to 90% on a weight basis and preferably, 20 to 80% by weight. The optimum yield of these compounds is likely to be obtained using the highest temperature in the preferred range at the lowest LHSV.
- the preferred catalyst is selected from the group consisting of monohydrogen phosphate of calcium, magnesium, zinc, mixtures of strontium and barium in the ratio of Sr to Ba of about 1 to 5 to 5 to 1 and mixtures of lanthanum and strontium in the ratio of La to Sr of about 15 to 1 to 15.
- the organic feed stock used in this reaction to produce TED A is a substituted piperazine compound selected from the group-consisting of hydroxyethylpiperazine and aminoethylpiperazine.
- the catalysts of this invention are relatively uneffected by the purity of the feed stock. For example, high conversion and good yields can be obtained from crude hydroxyethylpiperazine which contains minor quantities of piperazine and bis hydroxyethylpiperazine.
- the preferred catalyst is a mixture of strontium and nickel monohydrogen phosphate in the ratio of Sr to N i of about 1 to 5 to 5 to 1.
- the feed stock is morpholine and dimethylethanolamine in the molar ratio in the range of about 1 to 3 and 3 to 1.
- the reaction takes place in the presence of hydrogen in the molar ratio of hydrogen to organic feed of about 1 to 1 to 20'to 1 and an inert gas such as nitrogen, argon or helium in the molar ratio of inert gas to organic feed of about 1 to 1 to 20 to 1.
- diglycolamine compounds e.g. morpholine and alkyl morpholine, wherein the alkyl group has from 1 to 6 carbon atoms
- diglycolamine compounds e. ' g. diglycolamine and alkyl diglycolamines, wherein the alkyl group has from 1 to 6 carbon atoms
- This reaction also preferably takes place in the presence of the inert gas in ratios of 2 to 1 to 10 to 1 inert gas to liquid organic feed stock.
- the methods and catalysts of this invention are also capable cf reacting an alcohol and a nitrogen-containing compound selected from the group consisting of ammonia, aliphatic primary and secondary amines, and aromatic primaiy and secondary amines to selectively convert this ccmpound to the corresponding symmetrical or unsymmetrical higher molecular weight amine with little, if any, conversion to the corresponding by-products of thermodynamic amine equilibration.
- the amines and alcohol in the feed stock each contain 1 to 20 carbons per molecule.
- the catalyst is lanthanum or copper monohydrogen phosphate and the molar ratio of alcohol to nitrogen-containing compound ranges from about 1 to 6 to 6 to 1.
- the obtained product had a surface area of 10-15 m 2 / g.
- the principal component was identified as ⁇ -SrHPO 4 with minor quantities of Sr 5 (OH) (PO 4 ) 3 and unreacted Sr(N0 3 ) 2 .
- Infrared spectroscopy showed a spectrum consistent with SrHPO 4 .
- Example 2 The procedure for preparing the Example 2 was carried out except that 130 grams of Ba(N0 3 ) 2 and 106 grams of Sr(N0 3 ) 2 were dissolved in distilled water in place of the 195 and 53 grams respectively.
- the product had a surface pH of 4-5 and a Sr/Ba ratio of 2/1 mol/mol.
- the resulting catalyst was in the form of a fine powder and was deposited on an inert, low surface area Alundum silica-alumina core using a powder-coating step.
- the step comprised placing the amount of catalyst to be coated into a jar with the Alundum spheres and rotating on a jar-mill for several days to cause the catalyst powder to adhere to the spheres.
- the resulting coated spheres contained 25% of the active catalyst and 75% inert.
- Example 2 212 grams of Sr(N0 3 ) 2 were dissolved in distilled water and diluted to 500 cc. 115 grams of ammonium dihydrogen phosphate --NH4H2P04-- were dissolved in distilled water and diluted to 500 cc. The remaining steps of the catalyst procedure of Example 2 were carried out. The resulting catalyst was believed to contain less than 5% strontium dihydrogen phosphate --Sr(H 2 PO 4 ) 2 -- with the balance being SrHPO 4 . The surface pH of this catalyst mixture was 4-4.6 in comparison to substantially pure strontium monohydrogen phosphate which has a surface pH of 4.8-5.4. Substantially pure strontium dihydrogen phosphate was found to have a surface pH of 0.2-1.2; see Example 2 1.
- Example 1 The same procedure for preparing the catalyst of Example 1 was carried out except that 236 grams of calcium nitrate --Ca(NO 3 ) 2 .4H 2 O-- and 115 grams of NH 4 H 2 PO 4 were combined. The resulting dried catalyst particles were coated on the silica-alumina spheres in the same manner as that of Example 3.
- the analysis of the catalyst formed by this procedure indicated that it consisted essentially of calcium monodihydrogen phosphate with a Ca/P ratio of 1.009 and a surface pH of 4-6. In contrast, substantially pure calcium monohydrogen phosphate had a surface pH of 5-5.5; see Example 16 below. The presence of a very small amount of calcium dihydrogen phosphate may account for the difference in the surface pH value of this catalyst.
- Example 2 The catalyst preparation procedure of Example 2 was repeated except that 212 grams of Sr(N0 3 ) 2 were dissolved in place of the mixed barium and strontium nitrate salts and the resulting strontium monohydrogen phosphate catalyst had a surface pH of 4.8-5.2.
- the SrHPO 4 catalyst of Example 6 was heat treated for 2 hours in the presence of a mixture 20% by volume steam and the balance air at 350°C.
- the resulting strontium pyrophosphate (Sr2P207) had a crushing strength of 0 .47 kg./mm of length and a packed bulk density of 1.01 kg./l.
- Example 14 The ZnHP0 4 catalyst product of Example 14 above was coated on the silica-alumina spheres in the manner set forth in Example 3.
- Example 21 The fine powder of-the catalyst prepared in accordance with Example 21 was deposited on silica-alumina spheres in the manner set forth in Example 3.
- Precipitation of SrHPO 4 was effected by slowly adding the Na 2 HPO 4 solution to the Sr(N0 3 ) 2 solution with rapid stirring.
- the white SrHPO 4 precipitated rapidly from solution forming a rather thick slurry. This slurry was mixed for one hour, after which time the pH was measured to be about six.
- the solid SrHPO 4 was recovered by filtering on an eight frame filter press using cloth filters. It was washed with deionized water. After filtering and washing, the solid was dried in a circulating hot air oven at 250°F for four hours. The yield of SrHPO was 1680 grams. The solid was wetted and formed into pellets by extrusion through a 3.1 mm die plate and cutting the extrudates to about 1/4 inch in length. After drying the extrudate at 250°F for four hours in a circulating hot air oven, they were heat treated at 662°F for two hours in a 20% steam, 80% air atmosphere.
- Example 1 106 grams of Sr(NO 3 ) 2 and 145 grams of Ni (NO 3 ) 2 6H 2 0 were dissolved in distilled water and diluted to 500 cc. 132 grams of (NH 4 ) 2 HP0 4 were dissolved in distilled water and diluted to 500 cc. the remaining steps of Example 1 were carried out to yield a (Sr-Ni)HP0 4 catalyst having a surface pH of 5.4-7.0.
- Example 23 The catalyst of Example 23 was tested in the conversion of crude HEP to TEDA. The reaction was carried out at atmospheric pressure, at a liquid hourly space velocity of 0.3 and at the temperatures indicated in Table 3 below.
- the catalyst of Example 23 was tested for the conversion of diethanolamine to TEDA.
- the test was carried out at 370°C using a feed consisting of diethanolamine and water (2.0 to 1.0 mole ratio) pumped into the reactor at a rate of 4.4 liquid cc/hr along with helium diluent at a rate of 25 cc/minute.
- the diethanolamine was in completely converted to TEDA, as the only, i.e. about 26 mol. %, recovered product.
- a 64% by weight solution of N-aminoethyl piperazine in water was passed over a catalyst composition consisting essentially of SrHPO 4 at 380°C and at a liquid hourly space velocity of 0.3 volumes of liquid per volume of catalyst.
- a catalyst composition consisting essentially of SrHPO 4 at 380°C and at a liquid hourly space velocity of 0.3 volumes of liquid per volume of catalyst.
- a first pass operation there was obtained 96.8 mol. % conversion of the feed compound, obtaining a yield of 34.8% by weight (40.1 mol. %) TEDA and 27.1% by weight (40.6 mol. %) PIP.
- SrHPO 4 may be employed as a catalyst.
- Other typical condensation reactions in which SrHPO 4 may be employed as a catalyst include the formation of amines by amination of the corresponding alcohols with ammonia and the formation of polyamines from glycols and diamines.
- SrAPO 4 As a highly selective catalyst is due to the presence of a specific structure, which provides a narrow range of acidity.
- This narrow acidity range displayed by SrHPO 4 may be optimum for promoting certain types of acid catalyzed reactions, in contrast to such catalysts as alumina, silica-alumina and the like which have acid sites of widely varying strength, and hence show relatively low selectivity for the desired reaction.
- Diethyleneglycol was passed over the SrHP0 4 catalyst of Example 23 in the presence of water at a temperature of 370°C and at a contact time of 6.7 seconds.
- the feed contained 57 vol. % diethyleneglycol and 43 vol. % H 2 0.
- the reaction product contained 33 wt. % 1,4-dioxane, corresponding to a yield of 47 mol. %.
- the addition of water to the organic feeds may be desirable to prevent loss of catalyst activity as a result of dehydration of the SrHP04 to the pyrophosphate.
- the SrHPO 4 catalyst of Example 23 was tested for the conversion of 1, 4-butanediol to tetrahydrofuran. The test was carried out at 350°C using a feed consisting of 20 percent by volume of water and 80 percent by volume of 1, 4-butanediol pumped to the tubular reactor at a rate of 4.4 cc/hr. Helium dilutent was also fed at the rate of 30 cc/min. Under these conditions, the diol was completely converted to tetrahydrofuran.
- the CaHPO 4 catalyst of Example 5 was recovered in a fine, powdered state and was deposited on inert alumina spheres instead of the silica-alumina spheres in the same manner as set forth under Example 3.
- 20 cc of the resulting coated alumina contained 2 gms. of CaHP0 4 .
- the performance of this catalyst was evaluated for the preparation of an alipathic secondary amine with a feed mixture of monoethylamine (EA) and methanol using the general procedure used in Examples 25-62 for the preparation of TEDA. Specifically, 1 mol. of the primary amine and 1 mol. of the alcohol were reacted at 350°C, 1 atmosphere pressure and an LHSV of 0.15/hr. The conversion was 23.9 mol.
- the yield of methylethylamine (MEA) was 16.5 mol. % of the amine feed with a selectivity of 69 mol. %.
- the only other product in any significant quantity was dimethylethylamine (DMEA) with a yield of 5.4 mol. % and a selectivity of 22 mol %.
- Example 68 The procedure of Example 68 was followed except that 1 mol. of diethylamine (DEA) was substituted for 1 mol. of EA. 27.6 mol. % of this primary amine in the feed was converted for the most part to a single secondary amine, i.e. diethylmethylamine (DEMA) and a trace amount of a tertiary amine, i.e. triethylamine.
- the yield of DEA fed was 23 mol. % DEMA with a selectivity of 83.3 mol. %.
- the SrHPO 4 catalyst of Example 6 was used to convert methanol and either monoethylamine (Example 72) or diethylamine (Example 73) in the same manner set forth under Example 68.
- Example 13 The CuHPO 4 catalyst of Example 13 was coated onto alumina spheres and the procedure of Example 68 was followed except that 1 mol. of ammonia was substituted for 1 mol. of EA.
- the results from this reaction were a 65 mol. % yield of monomethylamine (MA) based on the methanol, an 87 mol.% selectivity to MA and a methanol conversion of 75 mol. %.
- MA monomethylamine
- Example 9 The La 2 (HP0 4 ) 3 catalyst of Example 9 was deposited on alumina spheres and the procedure of Example 74 was followed. The results were yields based on the methanol in the feed of 13 mol. % trimethylamine (TMA), 2.8 mol. % dimethylamine (DMA) and 3 mol. % monomethylamine (MA), selectivities based on the methanol of 69 mol. % TMA, 14.9 mol. % DMA and 16 mol. % MA, and a methanol conversion of 52 mol. %.
- TMA trimethylamine
- DMA dimethylamine
- MA monomethylamine
- MgHP0 4 and BaHPO 4 were effective in selectivity converting amines to the corresponding higher molecular weight amine.
- the (Sr-Ni)HP0 4 catalyst of Example 24 was evaluated for the preparation of N-(2-dimethylaminoethyl)morpholine (DMAEM) with a feed mixture of morpholine (MOR), dimethylethanolamine (DMEA), distilled water, hydrogen and helium in the amounts shown below in Table 5 using the general procedure used in Examples 25-62 for the TEDA preparation. Specifically the condensation reaction was carried out at 340°C, 1 atmosphere of'pressure and an LHSV in the range of 0.31-0.44/hr. as shown in Table 5 in the presence of 20 cc. of the (Sr-Ni)HPO 4 catalyst granules.
- Example 1 The catalyst product of Example 1 was evaluated for catalytic performance for the preparation of morpholine from diglycolamine at 1 atmosphere in accordance with the following test procedure:
- Example 87-91 The test procedure set forth in Examples 87-91 was followed in Examples 92-118 in the presence of the Example 1 catalyst.
- Table 7 below sets forth the feed mixture, operating conditions and the product yields for each example.
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Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US45130582A | 1982-12-20 | 1982-12-20 | |
US451305 | 1982-12-20 | ||
US06/451,295 US4446320A (en) | 1982-05-24 | 1982-12-20 | Morpholine compounds prepared via phosphate catalysts |
US451295 | 2006-06-12 |
Publications (1)
Publication Number | Publication Date |
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EP0111928A1 true EP0111928A1 (de) | 1984-06-27 |
Family
ID=27036315
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP83112839A Withdrawn EP0111928A1 (de) | 1982-12-20 | 1983-12-20 | Katalyse von Kondensationsreaktionen |
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EP (1) | EP0111928A1 (de) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0228898A2 (de) * | 1985-12-27 | 1987-07-15 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Verfahren zur Herstellung zyklischer Amine |
EP0230776A2 (de) * | 1985-12-27 | 1987-08-05 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Verfahren zur Herstellung zyklischer Amine |
US4725681A (en) * | 1985-08-19 | 1988-02-16 | Ethyl Corporation | Production of triethylenediamine |
EP0263463A2 (de) * | 1986-10-08 | 1988-04-13 | BASF Aktiengesellschaft | Verfahren zur Herstellung von 1,4-Diazabicyclo(2,2,2)-octanen |
EP1070717A1 (de) * | 1999-07-23 | 2001-01-24 | Basf Aktiengesellschaft | Verfahren zur Herstellung von reinem Triethylendiamin |
WO2002074755A1 (de) * | 2001-03-16 | 2002-09-26 | Basf Aktiengesellschaft | Verfahren zur herstellung von n-substituierten 2,6-dialkylmorpholinen |
US6552194B2 (en) | 2001-01-10 | 2003-04-22 | Basf Aktiengesellschaft | Process for the preparation of pure triethylenediamine (TEDA) |
US7074926B2 (en) | 2003-01-30 | 2006-07-11 | Basf Aktiengesellschaft | Decoloration and color stabilization of TEDA solution |
US7345173B2 (en) | 2001-05-10 | 2008-03-18 | Basf Se | Work-up of the mother liquor obtained in the preparation of high-purity triethylenediamine |
US7872131B2 (en) | 2004-05-15 | 2011-01-18 | Basf Se | Method for producing a solution of pure triethylenediamine (TEDA) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0069322B1 (de) * | 1981-06-29 | 1988-08-24 | Air Products And Chemicals, Inc. | Katalyse von Amin-Kondensationsreaktionen |
-
1983
- 1983-12-20 EP EP83112839A patent/EP0111928A1/de not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0069322B1 (de) * | 1981-06-29 | 1988-08-24 | Air Products And Chemicals, Inc. | Katalyse von Amin-Kondensationsreaktionen |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4725681A (en) * | 1985-08-19 | 1988-02-16 | Ethyl Corporation | Production of triethylenediamine |
EP0228898A2 (de) * | 1985-12-27 | 1987-07-15 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Verfahren zur Herstellung zyklischer Amine |
EP0230776A2 (de) * | 1985-12-27 | 1987-08-05 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Verfahren zur Herstellung zyklischer Amine |
EP0228898A3 (en) * | 1985-12-27 | 1988-01-07 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Catalyst for vapor-phase intramolecular dehydration reaction of alkanolamines |
EP0230776A3 (en) * | 1985-12-27 | 1988-01-07 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Catalyst for vapor-phase intermolecular dehydration reaction of alkanolamines |
EP0263463A3 (en) * | 1986-10-08 | 1989-08-09 | Basf Aktiengesellschaft | Process for the preparation of 1,4-diazabicycloû2,2,2¨ octanes |
EP0263463A2 (de) * | 1986-10-08 | 1988-04-13 | BASF Aktiengesellschaft | Verfahren zur Herstellung von 1,4-Diazabicyclo(2,2,2)-octanen |
EP1070717A1 (de) * | 1999-07-23 | 2001-01-24 | Basf Aktiengesellschaft | Verfahren zur Herstellung von reinem Triethylendiamin |
US6627756B1 (en) | 1999-07-23 | 2003-09-30 | Basf Aktiengesellschaft | Preparation of pure triethylenediamine |
US6552194B2 (en) | 2001-01-10 | 2003-04-22 | Basf Aktiengesellschaft | Process for the preparation of pure triethylenediamine (TEDA) |
WO2002074755A1 (de) * | 2001-03-16 | 2002-09-26 | Basf Aktiengesellschaft | Verfahren zur herstellung von n-substituierten 2,6-dialkylmorpholinen |
US7105662B2 (en) | 2001-03-16 | 2006-09-12 | Basf Akteingesellschaft | Method of producing N-substituted 2,6-dialkylmorpholines |
US7345173B2 (en) | 2001-05-10 | 2008-03-18 | Basf Se | Work-up of the mother liquor obtained in the preparation of high-purity triethylenediamine |
US7074926B2 (en) | 2003-01-30 | 2006-07-11 | Basf Aktiengesellschaft | Decoloration and color stabilization of TEDA solution |
US7872131B2 (en) | 2004-05-15 | 2011-01-18 | Basf Se | Method for producing a solution of pure triethylenediamine (TEDA) |
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